[16800-46-7]  · C9H9CrN3O3  · Tris(acetonitrile)tricarbonylchromium  · (MW 259.21)

(preparation of arene-chromium complexes1)

Physical Data: mp 135 °C (dec).

Solubility: sol THF, acetonitrile.

Form Supplied in: not commercially available.

Preparative Methods: by refluxing Hexacarbonylchromium in Acetonitrile in an inert atmosphere. Removal of solvent under an inert atmosphere yields tris(acetonitrile)tricarbonylchromium.2

Purification: the crude solid obtained in the above preparation is typically used without further purification.

Handling, Storage, and Precautions: air and thermally sensitive; pyrophoric. Use in a fume hood.

Preparation of Arene-Chromium Complexes.

Treatment of aromatic compounds with tris(acetonitrile)tricarbonylchromium in THF at 65 °C leads to the corresponding (arene)tricarbonylchromium complexes (eq 1),1 which are very useful reagents for the arylation of nucleophiles.3 Arene-chromium complexes can be produced at lower temperatures using tris(acetonitrile)tricarbonylchromium than in the conventional procedure using hexacarbonylchromium.4

Alkene Isomerization.

Tris(acetonitrile)tricarbonylchromium catalyzes the isomerization of 1-phenylindene to 3-phenylindene (eq 2).5 The scope and limitations of this reaction have not been tested.

Allylic Oxidation.

Treatment of alkenes with t-Butyl Hydroperoxide in the presence of catalytic amounts of tris(acetonitrile)tricarbonylchromium (generated in situ) affords the corresponding ketone in high yield (eq 3).6 The position of the alkene is unchanged during the oxidation.

Related Reagents.

Hexacarbonylchromium; (h6-Benzene)tricarbonylchromium.

1. Knox, G. R.; Leppard, D. G.; Pauson, P. L.; Watts, W. E. JOM 1972, 34, 347.
2. Tate, D. P.; Knipple, W. R.; Augl, J. M. IC 1962, 1, 433.
3. Semmelhack, M. F. In COS 1991, 4, 517.
4. Mahaffy, C. A. L.; Pauson, P. L. Inorg. Synth. 1979, 19, 154.
5. Berno, P.; Ceccon, A.; Gambaro, A.; Venzo, A. TL 1988, 29, 3489.
6. Pearson, A. J.; Chen, Y. S.; Hsu, S. Y.; Ray, T. TL 1984, 25, 1235.

James W. Herndon

University of Maryland, College Park, MD, USA

Copyright 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.